Department of Chemical Engineering, Hiroshima University, Higashi-Hiroshima 739-8527, Japan.
Langmuir. 2010 Jul 6;26(13):10897-905. doi: 10.1021/la100791j.
Nanoporous titania membranes with controlled pore sizes ranging from 0.7 to 2.5 nm, which had molecular weight cutoffs (MWCO) ranging from 500 to 2000, were successfully prepared by sol-gel processing, and the transport characteristics were evaluated across a temperature range of 30-80 degrees C. With increasing temperature, the permeate flux increased 2- to 3-fold, depending on the pore size. The water permeation mechanism was found to be different from viscous flow and was explained by the state of the water (free water/bound water/nonfreezing water) inside confined pores. The rejection of neutral solutes such as raffinose, the separation mechanism of which is molecular sieving (steric hindrance), decreased with temperature whereas that of electrolytes (MgCl(2) and NaCl), the separation mechanism of which is the charge effect (Donnan exclusion), was approximately constant. The temperature dependence of neutral and electrolyte solutes was analyzed using the Spiegler-Kedem equation by combining the Arrhenius equations for diffusivity and viscosity, which we obtained DeltaE(m), the activation energy of diffusion, after eliminating the effect of viscosity. For large DeltaE(m), which corresponds to the rejection of neutral solutes on the basis of molecular sieving, rejection decreased with temperature but remained unchanged for small DeltaE(m), which corresponds to the rejection of electrolytes based on the charge effect.
成功制备了孔径为 0.7 至 2.5nm、分子量截止值(MWCO)为 500 至 2000 的纳米多孔二氧化钛膜,其通过溶胶-凝胶工艺制备,并在 30 至 80°C 的温度范围内评估了其传输特性。随着温度的升高,渗透通量增加了 2 至 3 倍,这取决于孔径。发现水的渗透机制不同于粘性流动,并通过受限孔内水的状态(自由水/结合水/非冻结水)来解释。中性溶质如棉子糖的截留率随着温度的升高而降低,其分离机制是分子筛(空间位阻),而电解质(MgCl2 和 NaCl)的截留率则基本保持不变,其分离机制是电荷效应(Donnan 排斥)。通过将扩散和粘度的 Arrhenius 方程结合起来,使用 Spiegler-Kedem 方程分析了中性和电解质溶质的温度依赖性,我们消除了粘度的影响后得到了扩散的活化能ΔE(m)。对于大的ΔE(m),根据分子筛原理,中性溶质的截留率随温度降低而降低,但对于小的ΔE(m),根据电荷效应,电解质的截留率保持不变。